|Publication number||US5470904 A|
|Application number||US 08/190,287|
|Publication date||Nov 28, 1995|
|Filing date||Feb 2, 1994|
|Priority date||Jul 21, 1992|
|Also published as||CA2140652A1, CA2140652C, EP0652907A1, EP0652907A4, US5512623, US5686519, US5804633, WO1994002542A1|
|Publication number||08190287, 190287, US 5470904 A, US 5470904A, US-A-5470904, US5470904 A, US5470904A|
|Inventors||Rachel M. Loftin, Kimberly B. Sanborn|
|Original Assignee||The Gillette Company|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (26), Non-Patent Citations (11), Referenced by (13), Classifications (12), Legal Events (4)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This is a divisional of copending application Ser. No. 07/968,001, filed Oct. 28, 1992 pending which is a continuation in part of U.S. Ser. No. 07/917,455, filed Jul. 21, 1992, abandoned.
This invention relates to marking compositions.
Traditionally, permanent inks for use in markers have been provided in liquid form, as solvent-based or aqueous solutions. Solvent-based inks generally provide good adhesion and wetting on a wide variety of smooth, difficult to wet substrates, e.g., glass, plastic and metal. However, there is an increasing desire in the field to reduce or eliminate solvent use, due to environmental and safety concerns, and, secondarily, to avoid the unpleasant odor of solvent-based inks. Aqueous inks, formulated to replace solvent based inks, generally do not wet all substrates, particularly plastics, glass and metal, and are often not water-fast.
The invention features permanent aqueous marker inks that can be used to mark, e.g., paper, plastics, glass, and metal.
One aspect of the invention features an aqueous marker ink which includes a hydrocarbon surfactant, a fluorocarbon surfactant, a pigment, a film-forming acrylic polymer, and water. In preferred compositions, the acrylic polymer is provided in the form of an emulsion, and the acrylic is a thermoplastic acrylic, more preferably polymethyl methacrylate. Preferably, the hydrocarbon and fluorocarbon surfactants are provided in a weight ratio of about 1:1.
In another aspect, the invention features an aqueous marker ink which includes an alkylphenol ethoxylate surfactant, a fluorocarbon surfactant, a pigment, a film-forming polymer, and water. In preferred compositions, the alkylphenol ethoxylate surfactant is an octylphenol ethoxylate.
In a third aspect, the invention features an aqueous marker ink which includes a silicone surfactant, a film-forming polymer, a pigment, and water. In preferred compositions, the silicone surfactant is a siloxane or silane surfactant and the silicone surfactant is fluorinated. The compositions may further include a fluorocarbon and/or a hydrocarbon surfactant.
Preferred inks include, by weight, about 0.1 to 1, more preferably 0.2 to 0.6 percent of the surfactant(s), about 10 to 40, more preferably 20 to 30 percent of the film-forming polymer, about 2 to 8 percent pigment, and sufficient water to provide a viscosity of less than about 20 cps. The ink may also include a small quantity (preferably 1-10%) of a low (less than 5) carbon alcohol.
The invention also features a method of marking a substrate, e.g., glass, plastic or metal. The method includes the steps of providing a marker having a reservoir, the reservoir containing one of the featured inks, and making a mark with the marker on the substrate.
Preferred marker inks advantageously do not include any solvent The term "solvent", as used herein, refers to liquids which are defined as Volatile Organic Compounds (VOCs). Further, they are permanent, i.e., water-fast and fade resistant, and write well on a wide variety of substrates, including difficult to wet substrates such as glass, metal, and plastics, e.g., polypropylene, polyethylene and PVC film (SARAN film). Preferred inks have a surface tension of from about 18 to 34 dynes/cm.
Other features and advantages of the invention will be apparent from the Description of the Preferred Embodiments thereof, and from the claims.
Preferred marker inks include a surfactant, or combination of surfactants, to reduce the surface tension of the ink composition to less than about 35 dynes/cm, an acrylic film forming polymer, a water-dispersible pigment, a humectant, and water.
The surfactant(s) can be either: (a) a combination of fluorocarbon and hydrocarbon surfactants, (b) a silicone surfactant, or (c) a combination of a silicone surfactant and a fluorocarbon surfactant and/or a hydrocarbon surfactant. The total amount of the surfactant in the composition is preferably from about 0.1 to 1, more preferably 0.2 to 0.6 percent by weight. It is preferred that the amount of the surfactant(s) included, and the ratio of surfactants, if a combination is used, be selected so as to provide a composition having a surface tension between about 18 and 34 dynes/cm. Too little surfactant(s) may prevent the composition from properly wetting difficult substrates, while too much may cause the ink to "soak through" when used on paper.
In the embodiments in which a combination of fluorocarbon and hydrocarbon surfactants is used, the ratio of fluorocarbon surfactant to hydrocarbon surfactant is preferably about 1:1.
Suitable fluorocarbon surfactants include at least one aliphatic fluorocarbon group. Preferred fluorocarbon surfactants include ZONYL FSA and FSN fluorosurfactants, available from Dupont, which contain, respectively, lithium 3, [(1H,1H,2H,2H-fluoroalkyl)thio]proprionate and telomer B monoether with polyethylene glycol (CAS No. 65545-80-4). Other suitable surfactants are fluorinated alkyl alkoxylates, available from 3M under the tradename FLUORAD, e.g., FLUORAD FC-171 surfactant.
Hydrocarbon surfactants include at least one aliphatic group. Suitable hydrocarbon surfactants include alkylphenol ethoxylates in which the alkyl group has between 6 and 12 carbons. The preferred alkylphenyl ethoxylate is octylphenol ethoxylate, e.g., TRITON® X-100 non-ionic surfactant, available from Union Carbide, Danbury, Conn.
Suitable silicone surfactants include, silanes and siloxanes. Examples are polyoxyethylene modified polydimethylsiloxanes (referred to in the art as "silicone glycol copolymers"), e.g., DOW CORNING® Q2-5211 and Q2-5212 super-wetting agents, available from Dow Corning Corp., Midland, MI. Also preferred are fluorinated silicone surfactants, e.g., fluorinated polysilanes, available from Ecology Chemical Co., Watertown Mass., under the tradename LEVELENE 100.
The choice of surfactant will depend upon the properties desired from the ink, and cost and stability factors. Typically, the hydrocarbon/fluorocarbon combination provides wetting properties that are stable over a long storage period, while the silicone surfactant provides good wetting and allows the use of a single surfactant.
Enough pigment should be included in the ink to provide an adequate color intensity, but not so much that viscosity becomes excessively high. The preferred inks include between approximately 2% and 8% pigment by weight, more preferably between approximately 5% and 7%. Pigments that may be used in the invention include water dispersible pigments, and preferably the pigment is provided in the form of an aqueous dispersion, for accurate measurement and uniform mixing. Suitable dispersions include those available from Hoechst Celanese under the tradename FLEXONYL or HOSTAFINE, those available from KVK U.S.A. Inc. under the tradename PREDISOL, those available from Heucotech Ltd. under the tradename HEUCOSPERSE, those available from Nippon Keiko Kagaku, Ltd. under the tradename LUMIKOL, and those available from Mikuni Color Works, Inc. under the tradename TITICACA. The total amount of the pigment dispersion to be added will depend upon the solids level of the dispersion, and will be selected to give an effective amount of the pigment, as described above. It is preferred that the pigment have a relatively small particle size, preferably less than 0.5 micron, to prevent settling. The small particle size also is more suitable for use in capillary feed markers.
The acrylic polymer is preferably provided in the form of an emulsion. However, if desired, a water soluble acrylic may be used. Preferred acrylic polymers include thermoplastic acrylics, e.g., polymethacrylates, such as polymethyl methacrylate and other methyl acrylates. A preferred acrylic emulsion is RHOPLEX® AC-261 emulsion, available from Rohm and Haas Co., Philadelphia, Pa. Rhoplex AC 261 is an all-acrylic co-polymer combination, a butyl acrylate/methyl methacrylate blend having a low acid content, a molecular weight of around 1,000,000 and a glass transition temperature of between 15 and 20. The resin is thermoplastic and in use forms a film on the substrate by coalescence after the correction fluid is applied. Preferred compositions contain from about 20 to 30 weight percent of the acrylic polymer. Too much of the acrylic may result in undesirably high viscosity at an effective level of pigment, while too little may result in an ink having poor water resistance when dry.
Preferred humectants are glycols, such as diethylene or dipropylene glycol or glycerol. A more preferred humectant is propylene glycol. The humectant prevents dry-out of the marker when the cap is left off. Accordingly, too much may cause the ink to dry too slowly, while too little may not prevent drying out of the marker. Preferred compositions include from 1 to 25 weight percent of the humectant, preferably from about 5 to 15 weight percent.
Other conventional ingredients may be included in the composition, e.g., biocides.
Sufficient water should be included in the ink so that its Brookfield viscosity at 25° C. is less than about 20 cps, more preferably between about 2 cps and 10 cps. If the viscosity is too low, the composition may not contain effective amounts of the active ingredients. If the viscosity is too high, the ink may be too thick for practical use, particularly in capillary feed systems.
A preferred procedure for preparing the compositions of the invention is to provide the pigment in the form of a dispersion, add to this dispersion the super-wetting surfactant (if a blend of surfactants is used, these are preferably mixed prior to addition to the pigment dispersion), then add the humectant, the water, and, finally, the acrylic emulsion, mixing between each addition. The ingredients can be mixed using any conventional mixer, under conditions of relatively low shear.
The following examples illustrate the invention.
A series of ink compositions were prepared using the preferred procedure described above. The formulations for these compositions are given in Table 1. Each ink was tested by forming a line on a series of substrates (PVC film (SARAN wrap), polyethylene, polypropylene, metal, glass and cellophane tape) and observing whether the line dried without shrinkage and/or beading. Each ink formed a uniform line, without beading or shrinkage, on each of the test substrates.
TABLE 1______________________________________ Sample #Ingredient 1 2 3 4 5______________________________________HOSTAFINE TS Pigment 15dispers'nHOSTAFINE B-2G Pigment 15dispers'nFLEXONYL ACB Pigment 10 10dispers'nFLEXONYL AB26 Pigment 10dispers'nPropylene Glycol 10 10 10 10 10TRITON X-100 hydrocarbon 0.25 0.5surf.ZONYL FSA fluorocarbon surf. 0.25 0.25SUPERWETTER Q2-5212 0.5siliconeLEVELENE 100 hydrocarbon 1 0.5 0.5surf.bacteriocide 0.1 0.1 0.1 0.1 0.1RHOPLEX AC261 acrylic 50 50 50 50 50polymerwater 24 24 29 29 29______________________________________
Other embodiments are within the claim. For example, a small amount (less than 10%) of 2-propanol may be added to the ink to decrease the drying time. An example of such an ink is:
______________________________________Ingredients Weight Percentage______________________________________Hostifine Black 2 to 8% pigment weightPropylene glycol 2 to 10%Rhoplex AC261 50%Triton X-100 0.1 to 0.5%Zonyl FSA 0.1 to 0.5%2-Propanol 2 to 10%Suttocide A 0.1%______________________________________
Water is added to make up the difference to 100%.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3085912 *||Feb 24, 1960||Apr 16, 1963||Martin Marietta Corp||Method of permanently marking polytetrafluoroethylene|
|US3948668 *||Mar 15, 1974||Apr 6, 1976||E. I. Du Pont De Nemours And Company||Fluorocarbon-containing printing ink and process for image printing|
|US4108782 *||Apr 27, 1977||Aug 22, 1978||The Dow Chemical Company||Foaming and silt suspending agent|
|US4221601 *||Jan 6, 1977||Sep 9, 1980||Basf Farben & Fasern Ag||Packaged pigment pastes and process for coloring and toning water-diluted coating agents|
|US4545818 *||Oct 11, 1983||Oct 8, 1985||United Kingdom Atomic Energy Authority||Aqueous ink compositions for ball-point pens|
|US4711802 *||Aug 14, 1986||Dec 8, 1987||E. I. Du Pont De Nemours And Company||Aqueous ink for use on fluorocarbon surfaces|
|US4762875 *||Feb 17, 1987||Aug 9, 1988||Gold Marvin H||Water based printing inks for plastic and metal surfaces|
|US4853037 *||Oct 30, 1987||Aug 1, 1989||Hewlett-Packard Company||Low glycol inks for plain paper printing|
|US4880565 *||Apr 12, 1985||Nov 14, 1989||The Dow Chemical Company||Fluorine containing viscoelastic surfactants|
|US5019166 *||Jun 22, 1989||May 28, 1991||Xerox Corporation||Thermal ink jet compositions|
|US5089050 *||May 6, 1991||Feb 18, 1992||Ciba-Geigy Corporation||Inks containing a water soluble compound as a stabilizer particularly for ink jet printing|
|US5106416 *||Aug 28, 1991||Apr 21, 1992||Hewlett-Packard Company||Bleed alleviation using zwitterionic surfactants and cationic dyes|
|US5106417 *||Oct 22, 1990||Apr 21, 1992||Ciba-Geigy Corporation||Aqueous printing ink compositions for ink jet printing|
|US5114479 *||Jun 29, 1990||May 19, 1992||Basf Corporation||Dye-latex combinations and use in aqueous inks|
|US5131776 *||May 20, 1991||Jul 21, 1992||Binney & Smith Inc.||Aqueous permanent coloring composition for a marker|
|*||DE3024646A||Title not available|
|EP0044378A1 *||May 5, 1981||Jan 27, 1982||International Business Machines Corporation||An ink composition for ink jet printers|
|EP0264897A2 *||Oct 20, 1987||Apr 27, 1988||Ppg Industries, Inc.||Water reducible acrylic polymer for printing of paper and polyvinyl chloride|
|EP0294044A1 *||May 11, 1988||Dec 7, 1988||Dow Corning Corporation||Method of printing on plastic substrate using a water-based ink|
|EP0304887B1 *||Aug 24, 1988||May 6, 1992||Sakura Color Products Corporation||Erasable ink compositions|
|EP0322805B1 *||Dec 23, 1988||May 27, 1992||Sakura Color Products Corporation||Water base erasable ink compositions|
|EP0337705A2 *||Apr 10, 1989||Oct 18, 1989||Sericol Limited||Printing inks|
|EP0439026A2 *||Jan 10, 1991||Jul 31, 1991||Fox Valley Systems, Inc.||Non-flammable aerosol paint composition|
|GB1337467A *||Title not available|
|JPS59120667A *||Title not available|
|WO1988000961A1 *||Jul 30, 1987||Feb 11, 1988||Small Products Limited||Improvements in or relating to printing|
|1||*||3M, Industrial Chemical Products Divison; Fluorad Technical Information, Fluorochemical Surfactants , Fluorad Fluorochemical Surfactant FC 171; (Sep. 1987).|
|2||3M, Industrial Chemical Products Divison; Fluorad™ Technical Information, "Fluorochemical Surfactants", Fluorad™ Fluorochemical Surfactant FC-171; (Sep. 1987).|
|3||Brochure re: "Selecting and Evaluating Fluorosurfactants Criteria for Surfactant Selection".|
|4||*||Brochure re: Selecting and Evaluating Fluorosurfactants Criteria for Surfactant Selection .|
|5||*||Dow Corning Wright Corporation; Midland, Mich.; New Product Information Brochure re: Superwetting Agents.|
|6||DuPont Chemicals; Material Safety Data Sheet; "`Zonyl` FSN Fluorosurfactant" (Jan. 15, 1992).|
|7||*||DuPont Chemicals; Material Safety Data Sheet; Zonyl FSN Fluorosurfactant (Jan. 15, 1992).|
|8||Rohm and Haas Company, Philadelphia, Pa.; "Polymers, Resins and Monomers", Trade Sales (1986).|
|9||*||Rohm and Haas Company, Philadelphia, Pa.; Polymers, Resins and Monomers , Trade Sales (1986).|
|10||Union Carbide Chemicals and Plastics Company, Inc., Industrial Chemicals Division, Danbury, Conn.; Triton Surfactants, "Triton® Nonionic Surfactant X-100".|
|11||*||Union Carbide Chemicals and Plastics Company, Inc., Industrial Chemicals Division, Danbury, Conn.; Triton Surfactants, Triton Nonionic Surfactant X 100 .|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US5852075 *||Jun 2, 1997||Dec 22, 1998||E. I. Du Pont De Nemours And Company||Surfactant system for ink jet inks for printing on hydrophobic surfaces|
|US5865553 *||Aug 1, 1997||Feb 2, 1999||Conte S.A.||Liquid-ink writing instrument having a reservoir fitted with a system to prevent loss of priming|
|US5869564 *||Dec 21, 1994||Feb 9, 1999||International Business Machines Corporation||Ink composition|
|US6087416 *||Jul 22, 1998||Jul 11, 2000||E.I. Du Pont De Nemours And Company||Aqueous pigmented ink jet inks for printing on vinyls|
|US7964552 *||Nov 13, 2007||Jun 21, 2011||E. I. Du Pont De Nemours And Company||Fluorosurfactant with disproportionate effect|
|US20050139128 *||Dec 31, 2003||Jun 30, 2005||Sung Edward H.||Process for conditioning azo pigments|
|US20070162420 *||Feb 5, 2007||Jul 12, 2007||Oracle International Corporation||Techniques for automatically discovering a database device on a network|
|US20070203504 *||Feb 27, 2006||Aug 30, 2007||Blair Denny||Skin-marking devices and their use|
|US20080145329 *||Nov 13, 2007||Jun 19, 2008||Axel Hans-Joachim Herzog||Fluorosurfactant with disproportinate effect|
|US20080185418 *||Feb 1, 2007||Aug 7, 2008||Black & Decker Inc.||Multistage solenoid fastening device|
|US20090017202 *||Sep 29, 2008||Jan 15, 2009||Daniel Joseph E||Methods of Applying Coating Compositions|
|WO2005065298A2 *||Dec 29, 2004||Jul 21, 2005||Sun Chemical Corporation||Process for conditioning azo pigments|
|WO2005065298A3 *||Dec 29, 2004||Mar 29, 2007||Sun Chemical Corp||Process for conditioning azo pigments|
|U.S. Classification||524/462, 106/31.93, 106/31.72, 106/31.89, 524/263, 524/463, 401/198|
|International Classification||B43K8/02, C09D11/16|
|Cooperative Classification||Y10S260/38, C09D11/16|
|May 27, 1999||FPAY||Fee payment|
Year of fee payment: 4
|Jul 18, 2001||AS||Assignment|
Owner name: BEROL CORPORATION, ILLINOIS
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:THE GILLETTE COMPANY;REEL/FRAME:011987/0649
Effective date: 20001220
|Dec 26, 2002||FPAY||Fee payment|
Year of fee payment: 8
|May 29, 2007||FPAY||Fee payment|
Year of fee payment: 12